US10739285B2 - Evaluating method for coal and producing method for coke - Google Patents

Evaluating method for coal and producing method for coke Download PDF

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US10739285B2
US10739285B2 US15/553,049 US201615553049A US10739285B2 US 10739285 B2 US10739285 B2 US 10739285B2 US 201615553049 A US201615553049 A US 201615553049A US 10739285 B2 US10739285 B2 US 10739285B2
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coal
coke
coals
evaluating
amine
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US20180031501A1 (en
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Yusuke DOHI
Kiyoshi Fukada
Takashi Matsui
Mikiya NAGAYAMA
Narumi NANRI
Kazutoshi Hanada
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JFE Steel Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B45/00—Other details
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/005—After-treatment of coke, e.g. calcination desulfurization
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/02—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering
    • G01N25/04—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering of melting point; of freezing point; of softening point
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/22—Fuels; Explosives
    • G01N33/222—Solid fuels, e.g. coal
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/22—Fuels; Explosives
    • G01N33/225—Gaseous fuels, e.g. natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0259—Nitrogen containing compounds

Definitions

  • the present invention relates to an evaluating method for a coal used as a raw material for coke and a producing method for a coke by the carbonization of a coal blend including a coal evaluated by the evaluating method.
  • coke used in a blast furnace is required to have a high strength, it is desirable to use a coal having a high caking property as a raw material for coke.
  • all of mined coals do not have a high caking property; some of the mined coals may have a low caking property. Therefore, in common, plural types (brands) of coals having different properties are mixed together to form a coal blend, which is used as a raw material for coke.
  • the caking property of a coal is an essential property for producing coke, which causes the coal to be melted and solidified in the carbonization of the coal.
  • the caking property of a coal is determined on the basis of the properties of the coal when the coal is melted. Therefore, whether or not a brand of coal is suitable as a raw material for coke may be readily determined by effectively using a value on thermoplastic property (measured value or estimated value) of the coal as a measure.
  • Patent Literature 1 and Patent Literature 2 a method for measuring (evaluating) the thermoplasticity of a non- or slightly caking coal has been developed.
  • the fluidity of a coal is measured by a Gieseler plastometer method under the conditions where the rate of temperature rise is set to 5° C./min or more, which is higher than the rate of temperature rise (3° C./min) specified in JIS M 8801, since the fluidity of a coal increases with an increase in the rate of temperature rise.
  • Patent Literature 2 it is described in Patent Literature 2 that the usability of a non- or slightly caking coal as a raw material for coke may be readily determined by the method proposed in Patent Literature 2, because there is a good correlation between the maximum fluidity (MF) of the non- or slightly caking coal which is measured with an increased rate of temperature rise and the CSR (coke strength after CO 2 reaction) of a coke produced by the carbonization of a coal blend prepared by blending the non- or slightly caking coals.
  • MF maximum fluidity
  • CSR coke strength after CO 2 reaction
  • the estimated fluidity of a noncaking coal is determined as a value on thermoplastic property of the noncaking coal. It is described in Patent Literature 3 that, in the above method, the fluidity A of a caking coal and the fluidity B of a coal blend that includes a noncaking coal and the caking coal are measured, and the estimated fluidity D that makes the fluidity B when added to the fluidity A is considered to be a value on thermoplastic property of the noncaking coal.
  • Patent Literature 1 and Patent Literature 2 in which the fluidity of a coal is measured by a Gieseler plastometer method with an increased rate of temperature rise, are simple and easy, questions remain as to a correspondence between the fluidity and the coke strength; in Patent Literature 1, no mention is made of the relationship between the fluidity of a coal which is measured by a Gieseler plastometer method with an increased rate of temperature rise and the coke strength.
  • Patent Literature 2 It is described in Patent Literature 2 that there is a good correlation between the MF of a non- or slightly caking coal which is measured with an increased rate of temperature rise and the CSR (coke strength after CO 2 reaction) of a coke produced by the carbonization of a coal blend prepared by mixing the non- or slightly caking coal with a coal other than non- or slightly caking coal (hereinafter, referred to as “balance coal”).
  • the non- or slightly caking coals described in Examples of Patent Literature 2 are bituminous coals having a degree of coalification (mean maximum reflectance of vitrinite Ro) of 0.96 to 1.16, which are considerably limited examples. It is not clear whether the good correlation between the MF of a non- or slightly caking coal and the coke strength holds also in the case where a non- or slightly caking coal other than bituminous coal is used.
  • the method for determining the estimated fluidity of a noncaking coal which is described in Patent Literature 3 may not be valid for the above evaluation because it is known that the fluidity of a coal blend may be affected by the interaction between coals and the estimated fluidity of a noncaking coal may vary with the brand of a caking coal used in combination with the noncaking coal.
  • Patent Literature 4 discloses a fact that adding a primary or secondary amine including an aromatic ring to a coal used as a raw material for coke may enhance the fluidity of the coal. However, Patent Literature 4 does not relate to a technique for evaluating the thermoplasticity of a non- or slightly caking coal.
  • the present invention was made in light of the above-described issues. It is an object of the present invention to provide a method for accurately measuring the thermoplasticity of a coal (in particular, non- or slightly caking coal) whose thermoplasticity has been difficult to evaluate and determining whether the coal that is to be measured does not significantly reduce the coke strength when used for a coal blend.
  • An evaluating method for a coal used as a raw material for coke including: using a physical property value relating to a thermoplasticity of a coal as an index for evaluating the coal, wherein a primary or secondary amine including an aromatic ring have been added to the coal, thereby enhancing the thermoplasticity of the coal.
  • the present invention it is possible to determine a coal (in particular, a non- or slightly caking coal) for a coal blend capable of maintaining the coke strength at a high level.
  • FIG. 1 is a graph illustrating the relationship between the common logarithm values (log MF [log ddpm]) of the Gieseler maximum fluidity MF of the evaluated coals and the differences ⁇ DI (DI (150/50)[ ⁇ ]) each calculated by subtracting the drum strength of a coke prepared from a coal blend including a corresponding one of the evaluated coals from the drum strength of a coke prepared from a balance coal that is a portion of the coal blend excluding the evaluated coal.
  • FIG. 2 is a graph illustrating the relationship between the log MF values of coals which were measured with an increased rate of temperature rise and the ⁇ DI values.
  • FIG. 3 includes graphs each illustrating the relationship between the blending ratio [mass %] of each of the evaluated coals in a coal blend and the log MF of the coal blend.
  • FIG. 4 is a graph illustrating the relationship between the log MF (estimated log MF) values of the evaluated coals which were determined on the basis of the graphs included in FIG. 3 and the ⁇ DI values.
  • FIG. 5 is a graph illustrating the relationship between the log MF values of the evaluated coals which were measured after a pitch had been added to the coals and the ⁇ DI values.
  • FIG. 6 is a graph illustrating the relationship between the log MF values of the evaluated coals which were measured after an amine had been added to the coals and the ⁇ DI values.
  • FIG. 7 is a graph illustrating the relationship between the log MF values of the evaluated coals which were included in the respective coal blends and the ⁇ DI values.
  • FIG. 8 is, a graph illustrating the relationship between the log MF values of the evaluated coals which were measured after an amine had been added to the coals and the ⁇ DI values.
  • thermoplasticity of a non- or slightly caking coal The difficulty in measuring the thermoplasticity of a non- or slightly caking coal and determining whether the non- or slightly caking coal is capable of maintaining the coke strength at a high level in the related art is described below.
  • Coals A to D Four types of coals (Coals A to D) were prepared as examples of non- or slightly caking coals that are to be evaluated.
  • the mean maximum reflectance of vitrinite Ro, the volatile matter content VM, and the Gieseler maximum fluidity MF of each of Coals A to D were measured.
  • mean maximum reflectance of vitrinite Ro the method defined in JIS M 8816 was used.
  • volatile matter content VM the method defined in JIS M 8812 was used.
  • Gieseler maximum fluidity MF the method defined in JIS M 8801 was used.
  • Table 1 shows the Ro [%], VM [%, dry basis], and MF [ddpm] of each of Coals A to D.
  • Gieseler maximum fluidity MF in Table 1 Coals A, B, and D are noncaking coals, and Coal C is a slightly caking coal.
  • the impact of each of the non- or slightly caking coals (Coals A to D) on the coke strength which may occur when the non- or slightly caking coal is included in a coal blend was determined using a carbonization test oven.
  • the blending ratios of the non- or slightly caking coals in the respective coal blends were set to 20% by mass.
  • the balance coal used was a coal prepared by mixing plural brands of coals such that the weighted mean Ro of the coal which was weighted by the blending ratios of the coals was 1.03 and the mean of the common logarithms of MF (log MF) (mean weighted by the blending ratios of the coals) was 2.3.
  • Coals A to D were each mixed with the balance coal to form four types of coal blends.
  • the coal blends were each charged into a carbonization vessel such that the bulk density (based on dry weight) of the coal blend was 930 kg/m 3 . While the bulk density of a coal charged is about 700 to 800 kg/m 3 in the operation of a common coke oven in which a coal is charged from the upper part of the coke oven chamber, the carbonization test described herein was conducted under the conditions where the bulk density was relatively high in order to emphasize the differences among the coal blends.
  • Carbonization of a coal was performed for 6 hours in an electric furnace having a furnace temperature of 1050° C. with a 10-kg weight being placed on the carbonization vessel. Subsequently, the carbonized coal was removed from the electric furnace and cooled with nitrogen. Hereby, coke was prepared.
  • the coke was each rotated 150 times at a rotational speed of 15 rpm, and the mass proportion of coke particles having a diameter of 15 mm or more was measured.
  • the drum strength index DI(150/15) [ ⁇ ] calculated by multiplying the mass ratio relative to the coke that has not been rotated by 100 was used for evaluating the coke strength.
  • the balance coal was also carbonized alone as in the carbonization of the coal blends to form a coke.
  • the drum strength DI(150/15) [ ⁇ ] of the coke was determined.
  • each of the non- or slightly caking coals as a raw material for coke was evaluated on the basis of the difference ⁇ DI calculated by subtracting the drum strength of a coke prepared from only the balance coal from the drum strength of a coke prepared from a coal blend including the corresponding one of Coals A to D.
  • a negative ⁇ DI indicates that the addition of the non- or slightly caking coal reduced the coke strength compared with the coke prepared from only the balance coal.
  • FIG. 1 illustrates the relationship between the log MF values of Coals A to D and ⁇ DI values. Although the MF values of Coals A, B, and D are 0 (zero) ddpm, the log MF values of Coals A, B, and D are denoted as “0” for convenience in the graph of FIG. 1 .
  • the graph illustrated in FIG. 1 confirms that the strength of a coke prepared from a coal blend including at least Coal A, B, or D was smaller than that of a coke prepared from only the balance coal. It is also confirmed that, although the log MF values of the non- or slightly caking coals (Coals A to D) do not vary greatly, the amounts of reductions ( ⁇ DI of FIG. 1 ) in the plurality of strength of coke prepared from the coal blends compared with the strength of a coke prepared from only the balance coal, which did not include the non- or slightly caking coal, varied with the types of the non- or slightly caking coals included in the coal blends. This proves the difficulty in determining the impact of the type of non- or slightly caking coal on the coke strength only by measuring the physical property value (Gieseler maximum fluidity MF) of the non- or slightly caking coal which relates to thermoplasticity.
  • the physical property value Garnier maximum fluidity MF
  • Patent Literature 1 and Patent Literature 2 that are the related art, in which MF is measured with an increased rate of temperature rise was tested.
  • a Gieseler plastometer method a retort in which a coal sample is placed is immersed in a soldering bath maintained at 300° C. and heated at 3° C./min.
  • the inventors of the present invention immersed a retort including a coal sample placed therein was immersed in a soldering bath maintained at 550° C. in order to increase the rate of temperature rise and measured the fluidity of the coal sample.
  • the measurement of the temperature inside the sample heated under the above conditions confirmed that the rate of temperature rise was about 75° C./min.
  • FIG. 2 illustrates the relationship between log MF and coke strength.
  • the graph illustrated in FIG. 2 confirms the variation in fluidity among the brands of coal.
  • ⁇ DI did not increase with an increase in log MF. That is, a good positive correlation between log MF and ⁇ DI was not confirmed.
  • the Gieseler maximum fluidity MF of each of the coal blends was measured.
  • the Gieseler maximum fluidity MF of each of the coal blends was measured.
  • the blending ratio of Coals A to D is 0% by mass, the coal blend is composed of only Coal E or F.
  • the common logarithm log MF of the Gieseler maximum fluidity MF of the coal blend may be determined from the MF value described in Table 3.
  • FIG. 3 illustrates the relationship between the blending ratio [mass %] of each of Coals A to D in the coal blend and log MF [log ddpm] of the coal blend.
  • FIG. 3( a ) illustrates the relationship between the blending ratio of each of Coals A to D in a coal blend that included Coal E as a balance coal and the Gieseler maximum fluidity MF of the coal blend; and
  • FIG. 3( b ) illustrates the relationship between the blending ratio of each of Coals A to D in a coal blend that included Coal F as a balance coal and the Gieseler maximum fluidity MF of the coal blend.
  • the hollow dots shown in the graphs of FIGS. 3( a ) and 3( b ) are determined by plotting data obtained by the extrapolation of the sets of data on the blending ratios of Coals A to D that are 0%, 25%, and 50% by mass for each and the corresponding log MF values of Coals A to D. Since the coal blends having a blending ratio of 100% by mass is each composed of only a specific one of Coals A to D, the log MF values of the hollow dots are considered to be the log MF (estimated log MF) values of Coals A to D.
  • FIG. 4 illustrates the relationship between the estimated log MF values of Coals A to D and the differences ⁇ DI.
  • the graph of FIG. 4 does not confirm a correlation between the estimated log MF and the coke strength. This proves that it is even difficult to evaluate the impact of the type (Coals A to D) of a non- or slightly caking coal on the coke strength by estimating the Gieseler maximum fluidity of the non- or slightly caking coal by applying the contents of Patent Literature 3.
  • FIG. 5 illustrates the relationship between log MF and ⁇ DI.
  • the log MF values of the coals are denoted as 0 in the graph of FIG. 5 .
  • the graph of FIG. 5 also does not confirm a correlation between the log MF values and ⁇ DI values.
  • a primary or secondary amine including an aromatic ring is added to a non- or slightly caking coal that is to be evaluated in order to enhance the thermoplasticity of the non- or slightly caking coal, and the non- or slightly caking coal is evaluated by using, as a measure, a physical property value of the non- or slightly caking coal which relates to the enhanced thermoplasticity of the coal.
  • the primary or secondary amine including an aromatic ring is preferably N,N′-di-2-naphthyl-p-phenylenediamine.
  • the amine may also be a compound other than N,N′-di-2-naphthyl-p-phenylenediamine which is capable of enhancing the thermoplasticity (fluidity) of a coal when added to the coal.
  • Specific examples of such a compound include phenothiazine, carbazole, and N-phenyl-1-naphthylamine, which are described in Patent Literature 4 as examples.
  • the inventors of the present invention further studied amines capable of markedly enhancing the MF of a coal and the regularity and, as a result, found that an amine having a high boiling point enhances the thermoplasticity of a coal when added to the coal. It is considered that, the higher the boiling point of an amine, the larger the amount of amine that remains in the temperature range of 350° C. to 550° C., in which the thermoplasticity of the coal occurs, and the higher the accuracy of representing the thermoplasticity of the coal.
  • N,N′-di-2-naphthyl-p-phenylenediamine has a high boiling point.
  • thermoplasticity used in the test was Gieseler maximum fluidity MF measured by a Gieseler plastometer method defined in JIS M 8801.
  • the amine used in the test was N,N′-di-2-naphthyl-p-phenylenediamine described above.
  • the amine was added to each of Coals A to D in an amount corresponding to 5% or 10% by mass of the amount of coal in place of 5% or 10% by mass of the amount of coal, and the Gieseler maximum fluidity MF of the coal was measured.
  • Table 4 shows the Gieseler maximum fluidity MF values measured.
  • the MF values shown in Table 4 confirm that adding 10% by mass of the amine to a non- or slightly caking coal whose MF is not possible to be measured when the amine is not added to the coal enhances the thermoplasticity of the coal and makes it possible to measure the MF of the coal.
  • adding 5% by mass of the amine to a non- or slightly caking coal enhances the thermoplasticity of the coal to some extent but may fail to markedly enhance the thermoplasticity of the coal depending on the brand of the coal. In such a case, the MF of the coal may fail to be measured.
  • Plural coals were mixed together to form a coal (balance coal) having a weighted mean Ro of 1.03 and a weighted mean log MF of 2.3.
  • the balance coal was mixed with each of Coals A to D such that the blending ratio of Coals A to D was 20% by mass.
  • four types of coal blends were prepared. As in the preparation of the graph of FIG. 1 , a coke was prepared from each of the four coal blends, and the drum strength of the coke was measured. Another coke was prepared by the carbonization of only the balance coal, the drum strength thereof was measured, and ⁇ DI was determined.
  • the above coal blends did not include N,N′-di-2-naphthyl-p-phenylenediamine, which is capable of enhancing the thermoplasticity of a coal.
  • FIG. 6 illustrates the relationship between the log MF values of coals which were measured when 5% or 10% by mass of N,N′-di-2-naphthyl-p-phenylenediamine was added to the coals and corresponding ⁇ DI values.
  • the plotted dots corresponding to Coal B overlap each other, because the log MF of Coal B was 0 in either case where the amount of N,N′-di-2-naphthyl-p-phenylenediamine added to Coal B was 5% or 10% by mass.
  • the graph of FIG. 6 confirms a positive correlation between the Gieseler maximum fluidity of a non- or slightly caking coal which is measured after the amine has been added to the coal and the strength of a coke prepared from a coal blend that includes the coal.
  • the positive correlation therebetween indicates the possibility of determining the usability of a non- or slightly caking coal, whose value on thermoplastic property is difficult (or, impossible) to measure, as a raw material for coke on the basis of the fluidity of the coal which is measured after a primary or secondary amine including an aromatic ring has been added to the coal.
  • the inventors of the present invention conducted an additional test in which different types of non- or slightly caking coals were evaluated in order to verify the good positive correlation between the fluidity of a non- or slightly caking coal which is measured after a primary or secondary amine including an aromatic ring has been added to the coal and the strength of a coke prepared from a coal blend that includes the coal.
  • Table 5 shows the evaluated non- or slightly caking coals.
  • Coals G to I shown in Table 5 are slightly caking coals having a low Gieseler maximum fluidity MF.
  • the adjustment of the balance coal was made such that the blending ratio of a non- or slightly caking coal in each coal blend was 0% or 15% by mass and the average qualities of the coal blend were an average Ro of 1.05 and an average common logarithm of MF (log MF) of 2.5.
  • the coal blends were each charged into a carbonization vessel such that the bulk density (in terms of dry weight) of the coal blend was 725 kg/m 3 , at which a coal is charged from the upper portion of a coke oven chamber in a common operation.
  • each of the non- or slightly caking coals as a raw material for coke was evaluated on the basis of the difference ⁇ DI calculated by subtracting, from the drum strength of a coke prepared from a coal blend that included a specific one of Coals G to I, the drum strength of a coke prepared from a coal blend that did not include any of Coals G to I.
  • a negative ⁇ DI concerning a non- or slightly caking coal indicates that adding the coal to a coal blend reduced the strength of the resulting coke compared with a coke prepared from a coal blend that did not include any of Coals G to I.
  • FIG. 7 illustrates the relationship between the log MF values of Coals G to I and corresponding ⁇ DI values.
  • the graph of FIG. 7 shows that the strength of a coke prepared from a coal blend that included Coal H or I was smaller than the strength of a coke prepared from a coal blend that did not include Coal H or I. It is also confirmed that, as for the log MF values of the non- or slightly caking coals (Coals H and I), although Coal H had a smaller log MF value, the amount of reduction ( ⁇ DI of FIG.
  • the MF values shown in Table 6 confirm that adding 10% by mass of the amine to the coals increased the MF values of the coals compared with the MF values of the coals that did not include the amine, that is, adding the amine to the coals enhanced the thermoplasticity of the coals. It is also confirmed that the order of log MF values of the coals described in Table 6, which were measured after the amine had been added to the coals, is different from the order of log MF values of the coals described in Table 5.
  • FIG. 8 illustrates the relationship between the log MF values of the coals which were measured after 10% by mass of N,N′-di-2-naphthyl-p-phenylenediamine had been added to the coals and corresponding ⁇ DI values.
  • the graph of FIG. 8 confirms that, the larger the log MF of a coal which was measured after 10% by mass of N,N′-di-2-naphthyl-p-phenylenediamine had been added to the coal, the smaller the amount of reduction in ⁇ DI.
  • Patent Literature 4 Although it is described in Patent Literature 4 that adding a primary or secondary amine including an aromatic ring to a coal enhances the fluidity of the coal, it is not known that the suitability of a coal as a raw material for coke can be evaluated on the basis of the fluidity of the coal which is measured after a primary or secondary amine including an aromatic ring has been added to the coal.
  • the method according to embodiments of the present invention makes it possible to evaluate the suitability of a coal which has been impossible to evaluate in the related art and to clearly determine whether or not the coal is usable as a raw material for coke.
  • the usability of the evaluated coal as a raw material for coke may be determined in the following manner.
  • the usability of a coal in particular, a non- or slightly caking coal
  • a coal in particular, a non- or slightly caking coal
  • a relational formula between the physical property value relating to thermoplasticity of a coal and the coke strength can be determined from the plural sets of data.
  • the relational formula may be determined by, for example, drawing a calibration curve by the method of least squares or freehand on the graph of FIG. 6 or 8 .
  • a physical property value of a coal which corresponds to the target coke strength ( ⁇ DI) is determined using the relational formula derived in [I] above.
  • the target coke strength is the strength of a coke that can be used in the operation of a blast furnace and can be determined in advance.
  • the difference e.g., ⁇ DI
  • the strength of a coke prepared from a coal blend including a non- or slightly caking coal can be estimated on the basis of the sets of data obtained by a carbonization test.
  • the physical property value relating to thermoplasticity of a coal that is to be measured is measured.
  • a coke prepared from a coal blend including the coal is considered to have a suitable coke strength.
  • a coke prepared from the coal blend is expected to have a coke strength larger than the predetermined target strength.
  • thermoplasticity of a non- or slightly caking coal may fail to be enhanced to a sufficient level and, as a result, the accuracy of the evaluation of the thermoplasticity of the coal may be degraded.
  • there is a suitable ratio at which the amine is added to a non- or slightly caking coal in order to enhance the thermoplasticity of the coal depending on the types of amine and non- or slightly caking coal used.
  • the inventors of the present invention studied a method for determining an amount of amine which is optimum for enhancing the thermoplasticity of a non- or slightly caking coal, which varies with the type of amine and the brand of non- or slightly caking coal.
  • the type and amount of amine added to a non- or slightly caking coal are determined in the following manner.
  • An amine capable of enhancing the fluidity of a coal when added to the coal is selected as an amine that is to be used.
  • the selected amine is added to plural types of coals (preferably, noncaking coals having an MF of 0) that are to be evaluated in a predetermined amount.
  • the MF values of the coals are subsequently measured.
  • the specific amount of amine is added to a non- or slightly caking coal, a physical property value of the coal which relates to thermoplasticity is measured, and the usability of the coal as a raw material for coke may be evaluated by using the measured physical property value as a measure.
  • the coal to which the amine is added is preferably a non- or slightly caking coal having a Gieseler maximum fluidity MF of 20 ddpm or less.
  • coals having a Gieseler maximum fluidity MF of 0 ddpm are referred to as noncaking coals
  • coals having a Gieseler maximum fluidity MF of about 100 ddpm or less are referred to as slightly caking coals. Since Gieseler maximum fluidity measured by the JIS method is an integer, the accuracy of measurement is low when MF is 10 ddpm or less. Therefore, applying the method according to the present invention to a coal having an MF of 10 ddpm or less is particularly advantageous.
  • the target to be evaluated in the present invention is a coal having a relatively small Gieseler maximum fluidity MF (MF 20 ddpm) whose thermoplasticity can be markedly enhanced when an amine is added to the coal.
  • thermoplasticity used in the above-described embodiment is Gieseler maximum fluidity MF
  • the physical property value relating to thermoplasticity used in the present invention is not limited to Gieseler maximum fluidity MF.
  • thermoplastic physical properties include the dilatability, adhesiveness, permeability, and viscosity of a melted coal.
  • specific examples of the physical property values include total dilatation measured with a dilatometer, specific dilatation volume, permeation distance, and viscoelasticity.
  • the evaluating method according to the present invention makes it possible to evaluate the impact of a non- or slightly caking coal on the strength of a coke prepared from a coal blend including the non- or slightly caking coal. This makes it possible to determine a coal (non- or slightly caking coal) for a coal blend that is capable of maintaining high coke strength.

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CN110793994B (zh) * 2019-09-16 2022-02-22 河南中鸿集团煤化有限公司 一种检验焦炉空压密封修补料性能的方法
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WO2024202184A1 (fr) * 2023-03-28 2024-10-03 Ｊｆｅスチール株式会社 Procédé d'estimation de la résistance du coke et procédé de production de coke

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60144386A (ja) 1983-12-30 1985-07-30 Nippon Steel Chem Co Ltd 石炭の乾留方法
JPS61285286A (ja) 1985-06-12 1986-12-16 Nippon Steel Chem Co Ltd 石炭の乾留方法
JPS62285051A (ja) 1986-06-03 1987-12-10 Mitsubishi Chem Ind Ltd 石炭の流動性測定方法
JPH039991A (ja) 1989-06-06 1991-01-17 Nkk Corp 非粘結炭の見掛けの流動度推定方法
JP2000073070A (ja) 1998-08-27 2000-03-07 Sumitomo Metal Ind Ltd 石炭の流動度測定方法ならびに原料炭の配合方法
EP1026223A1 (fr) 1998-07-29 2000-08-09 Kawasaki Steel Corporation Procede de production de coke metallurgique
JP2009249596A (ja) 2008-04-10 2009-10-29 Sumitomo Metal Ind Ltd コークスの製造方法
TW201217768A (en) 2010-09-01 2012-05-01 Jfe Steel Corp to manufacture high strength coke by setting novel formulation standard for coal
CN102559227A (zh) 2010-12-10 2012-07-11 上海梅山钢铁股份有限公司 利用基氏流动度指标进行配煤炼焦的方法
CN103189474A (zh) 2010-09-01 2013-07-03 杰富意钢铁株式会社 冶金用焦炭的制造方法以及用于制造冶金用焦炭的粘结材料
JP2014043545A (ja) 2012-03-08 2014-03-13 Jfe Steel Corp 石炭の改質方法及びコークスの製造方法
US20140144071A1 (en) 2010-09-01 2014-05-29 Jfe Steel Corporation Method for evaluating thermal plasticity of coals and caking additives, and method for producing coke
JP2015040270A (ja) 2013-08-23 2015-03-02 Ｊｆｅスチール株式会社 コークスの製造方法、コークス、改質石炭、改質配合炭および石炭もしくは配合炭の改質方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB747171A (en) * 1950-05-04 1956-03-28 C U R A Patents Ltd Manufacture of bodies composed of carbon in a chemically reactive state
CN100412166C (zh) * 2006-11-22 2008-08-20 北京金源化学集团有限公司 一种提高焦炭产量和性能的煤炭添加剂和方法
CN101585453B (zh) * 2008-05-20 2014-05-07 上海海事大学 集装箱码头出口箱堆场自动分配方法

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60144386A (ja) 1983-12-30 1985-07-30 Nippon Steel Chem Co Ltd 石炭の乾留方法
JPS61285286A (ja) 1985-06-12 1986-12-16 Nippon Steel Chem Co Ltd 石炭の乾留方法
JPS62285051A (ja) 1986-06-03 1987-12-10 Mitsubishi Chem Ind Ltd 石炭の流動性測定方法
JPH039991A (ja) 1989-06-06 1991-01-17 Nkk Corp 非粘結炭の見掛けの流動度推定方法
EP1026223A1 (fr) 1998-07-29 2000-08-09 Kawasaki Steel Corporation Procede de production de coke metallurgique
CN1286722A (zh) 1998-07-29 2001-03-07 川崎制铁株式会社 冶金用焦炭的制造方法
US6830660B1 (en) * 1998-07-29 2004-12-14 Jfe Steel Corporation Method for producing metallurgical coke
JP2000073070A (ja) 1998-08-27 2000-03-07 Sumitomo Metal Ind Ltd 石炭の流動度測定方法ならびに原料炭の配合方法
JP2009249596A (ja) 2008-04-10 2009-10-29 Sumitomo Metal Ind Ltd コークスの製造方法
TW201217768A (en) 2010-09-01 2012-05-01 Jfe Steel Corp to manufacture high strength coke by setting novel formulation standard for coal
CN103189474A (zh) 2010-09-01 2013-07-03 杰富意钢铁株式会社 冶金用焦炭的制造方法以及用于制造冶金用焦炭的粘结材料
US20140144071A1 (en) 2010-09-01 2014-05-29 Jfe Steel Corporation Method for evaluating thermal plasticity of coals and caking additives, and method for producing coke
RU2013114317A (ru) 2010-09-01 2014-10-10 ДжФЕ СТИЛ КОРПОРЕЙШН Способ оценки термопластичности углей и коксующих добавок и способ получения кокса
US9340740B2 (en) 2010-09-01 2016-05-17 Jfe Steel Corporation Method for evaluating thermal plasticity of coals and caking additives, and method for producing coke
CN102559227A (zh) 2010-12-10 2012-07-11 上海梅山钢铁股份有限公司 利用基氏流动度指标进行配煤炼焦的方法
JP2014043545A (ja) 2012-03-08 2014-03-13 Jfe Steel Corp 石炭の改質方法及びコークスの製造方法
JP2015040270A (ja) 2013-08-23 2015-03-02 Ｊｆｅスチール株式会社 コークスの製造方法、コークス、改質石炭、改質配合炭および石炭もしくは配合炭の改質方法

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
ChemicalBook.com, "N,N′-di-2-naphthyl-phenylenediamine", Sep. 15, 2013 (date obtained from Wayback Machine), Available online at: https://web.archive.org/web/20130915072619/https://www.chemicalbook.com/ChemicalProductProperty_En_CB4242789.htm (Year : 2013). *
Chinese Office Action for Chinese Application No. 201680011656.0, dated Aug. 26, 2019 with Concise Statement of Relevance of Office Action, 8 pages.
Chinese Office Action for Chinese Application No. 201680011656.0, dated Mar. 30, 2020, with Concise Statement of Relevance of Office Action, 7 pages.
Communication Pursuant to Article 94(3) for European Application No. 16 754 943.5, dated Mar. 4, 2019, 5 pages.
Extended European Search Report for European Application No. 16 754 943.5, dated Jan. 25, 2018, 8 pages.
First Chinese Search Report for Chinese Application No. 201680011656.0, dated Aug. 16, 2019, 1 page.
Human translation of Kojima (JP S60-144386 A) obtained from the USPTO. *
International Search Report and Written Opinion for International Application No. PCT/JP2016/000808, dated Apr. 12, 2016-6 Pages.
International Search Report and Written Opinion for International Application No. PCT/JP2016/000808, dated Apr. 12, 2016—6 Pages.
Japanese Office Action for Japanese Application No. 2017-050781, dated Dec. 10, 2019 with Concise Statement of Relevance of Office Action, 3 pages.
Korean Office Action for Korean Application No. 10-2017-7022813, dated Jun. 11, 2018, with Concise Statement of Relevance of Office Action, 7 pages.
Russian Office Action for Russian Application No. 2017129805/05, dated Jun. 1, 2018, with Concise Statement of Search Report, 9 pages.
Taiwanese Office Action for Taiwanese Application No. 105105461, dated Dec. 12, 2016, including Concise Statement of Search Report, 8 pages.

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